As a novel type of nanocellulose material, cellulose nanospheres (CNSs) have gained significant attention and rapid development in recent years. In this work, the surface hydrophobic modification of CNSs was achieved by employing maleic anhydride as an esterifying agent. The effects of modified cellulose nanospheres (CNS-MA) on the crystallization and hydrolysis behaviors of polylactic acid (PLA)-based composites were systematically investigated. The results demonstrate that surface modification improves the dispersion of CNSs in the PLA matrix. Well-dispersed particles act as nucleation sites, which increases the crystallization rate and crystallinity of PLA and endows the composites with remarkable heat distortion resistance. The storage modulus of the PLA/CNS-MA composites exceeds 300 MPa, even at an elevated temperature of 90 °C. Furthermore, the hydrolytic degradation of PLA is dramatically accelerated with the addition of CNS-MA. Combining the morphology observations and theoretical calculations, it is speculated that the fast hydrolytic degradation is related to a transition in the main hydrolytic degradation mechanism from surface erosion to bulk erosion, because the presence of CNS-MA provides particular pathways for water molecules to diffuse into the interior of the composites. This research highlights the potential of CNSs as a multifunctional filler with both reinforcing and degradation-promoting effects, offering valuable insights for the study of other biomass nanomaterials.
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